Catalytic composite, method of manufacture and process for use

ABSTRACT

Disclosed are a metal chelate-alkali metal hydroxide-quaternary ammonium hydroxide, catalytic composite, a method of manufacturing the catalytic composite, and a process of treating sour petroleum distillates utilizing the catalytic composite. The catalytic composite comprises a metal chelate, a quaternary ammonium hydroxide, and an alkaline metal hydroxide disposed on a molecular sieve, the alkali metal hydroxide comprising at least about 10 wt. % of the catalytic composite. The method of manufacturing the catalytic composite comprises contacting a molecular sieve with a metal chelate, a quaternary ammonium hydroxide, and a mixture of alkali metal hydroxide and at least one solvent selected from the group consisting of water and alcohols with fewer than 6 carbon atoms, the alkali metal hydroxide comprising a sufficient portion of said mixture such that said alkali metal hydroxide comprises at least about 10 wt. % of said resulting catalytic composite. The method of treating sour petroleum distillates comprises contacting the distillates at oxidation conditions with the catalytic composite described above.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The field of art to which the claimed invention pertains is catalyticcomposites and process useful for treating sour petroleum distillates.More specifically, the claimed invention relates to catalysts andcatalytic processes especially useful for the treatment of sourpetroleum distillates to effect the oxidation of mercaptans in thedistillate to disulfides.

2. Description of the Prior Art

Processes for treatment of sour petroleum distillates wherein thedistillate is treated in contact with an oxidation catalyst in thepresence of an oxidizing agent at alkaline reaction conditions havebecome well known and widely practiced in the petroleum refiningindustry. Said processes are typically designed to effect the oxidationof offensive mercaptans contained in a sour petroleum distillate withthe formation of innocuous disulfides--a process commonly referred to assweetening. The oxidizing agent is most often air. Gasoline, includingnatural, straight run and cracked gasolines, is the most frequentlytreated sour petroleum distillate. Other sour petroleum distillatesinclude the normally gaseous petroleum fraction as well as naphtha,kerosene, jet fuel, fuel oil, lube oil, and the like.

A commonly used continuous process for treating sour petroleumdistillates entails treating the distillate in contact with a metalphthalocyanine catalyst dispersed in an aqueous caustic solution toyield a doctor sweet product. The sour distillate and thecatalyst-containing aqueous caustic solution provide a liquid-liquidsystem wherein mercaptans are converted to disulfides at the interfaceof the immiscible solutions in the presence of an oxidizingagent--usually air. Sour petroleum distillates containing moredifficultly oxidizable mercaptans are more effectively treated incontact with a metal chelate catalyst disposed on a high surface areaadsorptive support--usually a metal phthalocyanine on an activatedcharcoal. The distillate is treated in contact with the supported metalchelate catalyst at oxidation conditions in the presence of an alkalineagent. One such process is described in U.S. Pat. No. 2,988,500. Theoxidizing agent is most often air admixed with the distillate to betreated, and the alkaline agent is most often an aqueous causticsolution charged continuously to the process or intermittently asrequired to maintain the catalyst in a caustic-wetted state.

Heretofore, the practice of catalytically treating mercaptan-containingsour petroleum distillates has involved the introduction of alkalineagents, usually sodium hydroxide, into the sour petroleum distillateprior to or during the treating operation. (U.S. Pat. No. 3,108,081,U.S. Pat. No. 4,156,641.) The prior art also suggests the addition tothe petroleum distillate along with certain alkaline agents of certainnon-alkaline additives. (U.S. Pat. No. 4,124,493, U.S. Pat. No.4,033,860.) In addition, the prior art suggests the use in an alkalineenvironment of certain catalytic composites produced from metalphthalocyanine solutions containing certain non-alkaline additives.(U.S. Pat. No. 4,087,378, U.S. Pat. No. 4,124,531.) The prior art alsosuggest the use of certain chemicals, including sodium hydroxide, toincrease the solubility of metal phthalocyanine in aqueous solutionsfrom which metal phthalocyanine catalysts to be used in alkalineenvironments are made. (U.S. Pat. No. 3,108,081.) The prior art does notdisclose or suggest the treating of a mercaptan-containing sourpetroleum distillate by contacting the distillate at oxidationconditions with an oxidizing agent and a catalytic composite comprisinga metal chelate, an alkali metal hydroxide, and a quaternary ammoniumhydroxide, disposed on a molecular sieve support. The catalyticcomposite of this invention can be used in the treating process of thisinvention with or without the necessity of addition of an alkalineagent. The consequent savings in materials handling and storageexpenses, and avoidance of use of hazardous alkaline chemicals in thetreating process, have been long desired.

SUMMARY OF THE INVENTION

It is a broad objective of my invention to present a novel catalyticcomposite and method for treating sour petroleum distillates.

In one of its broad aspects, the present invention embodies a catalyticcomposite comprising a metal chelate, an alkali metal hydroxide, and aquaternary ammonium hydroxide disposed on a molecular sieve support,said quaternary ammonium hydroxide represented by the structuralformula: ##STR1## wherein R is a hydrocarbon radical containing up toabout 20 carbon atoms and selected from the group consisting of alkyl,cycloalkyl, aryl, alkaryl and aralkyl, and R' is a substantiallystraight-chain alkyl radical containing from about 5 to about 20 carbonatoms, said alkali metal hydroxide comprising at least about 10 wt. % ofsaid catalytic composite.

In another of its broad aspects, the present invention embodies a methodof treating a mercaptan-containing sour petroleum distillate bycontacting said distillate at oxidation conditions in the presence of anoxidizing agent with the catalytic composite described in the precedingparagraph.

In a third broad aspect, the present invention embodies a method ofmanufacturing a catalytic composite which comprises contacting amolecular sieve support with a metal chelate and a quaternary ammoniumhydroxide represented by the structural formula: ##STR2## wherein R is ahydrocarbon radical containing up to about 20 carbon atoms and selectedfrom the group consisting of alkyl, cycloalkyl, aryl, alkaryl andaralkyl, and R' is a substantially straight-chain alkyl radicalcontaining from about 5 to about 20 carbon atoms, and with a mixture ofalkali metal hydroxide and at least one solvent selected from the groupconsisting of water and alcohols with fewer than six carbon atoms, saidalkali metal hydroxide being present in such amount that said alkalimetal hydroxide comprises at least about 10 wt. % of said catalyticcomposite.

Other objects and embodiments of this invention will become apparent inthe following detailed description.

DESCRIPTION OF THE INVENTION

The molecular sieves used in this invention may be any of various types.Molecular sieves are crystalline metal aluminosilicates with athree-dimensional interconnecting network structure of silica andalumina tetrahedra. The tetrahedra are formed by four oxygen atomssurrounding a silicon or aluminum atoms. Each oxygen atom has twonegative charges and each silicon has four positive charges. Thisstructure permits an ordered sharing arrangement, building tetrahedrauniforming in four directions.

In the crystalline structure, up to half of the quadrivalent siliconatoms can be replaced by trivalent aluminum atoms. By regulating theratios of the starting materials, it is possible to produce molecularsieves containing different ratios of silicon to aluminum ions anddifferent crystal structures containing various cations.

In the most common commercial molecular sieve, Type A, the tetrahedraare grouped to form a truncated octahedron with a silica or aluminatetrahedron at each point. This structure is known as a sodalite cage.

When sodalite cages are stacked in simple cubic forms, the result is anetwork of cavities approximately 11.5 A in diameter, accessible throughopenings on all six sides. These openings are surrounded by eight oxygenions. In the sodium form, this ring of oxygen ions provides an opening"window" of 4.2 A in diameter into the interior of the structure. Thesoda form of this crystalline structure is represented chemically by thefollowing formula:

    Na.sub.12 [(AlO.sub.2).sub.12 (SiO.sub.2).sub.12 ]X H.sub.2 O

The water of hydration which fills the cavities during crystallizationis loosely bound and can be removed by moderate heating. The number ofwater molecules in the structure can be as great as 27, making the waterin the saturated formula 28.5% of the weight of the anhydrous molecularsieve. Molecular sieves can be readily produced with other metalssubstituting for a portion of the sodium.

The crystal structure of the Type X molecular sieve is built up byarranging the basic sodalite cages in a tetrahedral stacking withbridging across the six-membered oxygen atoms ring. These rings provideopenings "windows" 9-10 A in diameter into the interior of thestructure. The overall electrical charge is balanced by positivelycharged cation(s), as in the Type A structure. The chemical formula thatrepresents the unit cell of Type X molecular sieve in the soda form isshown below:

    Na.sub.86 [(AlO.sub.2).sub.36 (SiO.sub.2).sub.106 ]X H.sub.2 O

As in the case of the Type A crystal, water of hydration can be removedby moderate heating. The value of X can be as great as 276, making thewater in this type of molecular sieve 35% of the weight of the anhydrousmolecular sieve.

The preferred form of molecular sieve for this invention is a Type Xmolecular sieve. Especially preferred is an anhydrous Type X molecularsieve with a nominal pore size of 10 angstroms. Also especiallypreferred is a Type X molecular sieve of the soda form.

Any of the hydroxides of the metals of Group I-A of the PeriodicChart--the alkali metal hydroxides--can be used as a component of thisinvention. The alkali metal hydroxide component of this invention can bea single alkali metal hydroxide, or a mixture of two or more alkalimetal hydroxides. The preferred alkali metal hydroxide for thisinvention is sodium hydroxide. Potassium hydroxide is also preferred.The alkali metal hydroxides are widely available commercially. They maybe made by the electrolysis of aqueous alkali-salt solutions, usuallythe chloride salt, or by the hydration of alkali metal hydrides.

The metal chelate employed in the practice of this invention can be anyof the various metal chelates known to the treating art as effective tocatalyze the oxidation of mercaptans contained in a sour petroleumdistillate with the formation of polysulfide oxidation products. Saidmetal chelates include the metal compounds of tetrapyridinoporphyrazinedescribed in U.S. Pat. No. 3,980,582, e.g. cobalttetrapyridinoporphyrazine; porphyrin and metaloporphyrin catalysts asdescribed in U.S. Pat. No. 2,966,453, e.g. cobalt tetraphenylporphyrinsulfonate; corrinoid catalysts as described in U.S. Pat. No. 3,252,892,e.g. cobalt corrin sulfonate; chelate organometallic catalysts such asdescribed in U.S. Pat. No. 2,918,426, e.g. the condensation product ofan aminophenol and a metal of Group VIII; and the like. Metalphthalocyanines are a preferred class of metal chelates.

The metal phthalocyanines which can be employed to catalyze theoxidation of mercaptans generally include magnesium phthalocyanine,titanium phthalocyanine, hafnium phthalocyanine, vanadiumphthalocyanine, tantalum phthalocyanine, molybdenum phthalocyanine,manganese phthalocyanine, iron phthalocyanine, cobalt phthalocyanine,platinum phthalocyanine, palladium phthalocyanine, copperphthalocyanine, silver phthalocyanine, zinc phthalocyanine, tinphthalocyanine and the like. Cobalt phthalocyanine and vanadiumphthalocyanine are particularly preferred. The metal phthalocyanine ismost frequently employed as a derivative thereof, the commerciallyavailable sulfonated derivatives, e.g. cobalt phthalocyaninemonosulfonate, cobalt phthalocyanine disulfonate or a mixture thereofbeing particularly preferred. The sulfonated derivatives may beprepared, for example, by reacting cobalt, vanadium or other metalphthalocyanine with fuming sulfuric acid. While the sulfonatedderivatives are preferred, it is understood that other derivatives,particularly the carboxylated derivatives, may be employed. Thecarboxylated derivatives are readily prepared by the action oftrichloroacetic acid on the metal phthalocyanine.

The quaternary ammonium hydroxide component of the catalytic compositeof this invention is represented by the structural formula: ##STR3##Wherein R is hydrocarbon radical containing up to about 20 carbon atomsand selected from the group consisting of alkyl, cycloalkyl, aryl,alkaryl and aralkyl and R' is a substantially straight-chain alkylradical containing from about 5 to about 20 carbon atoms. It ispreferred that one R radical be an alkyl radical containing from about12 to about 18 carbon atoms, and another R radical be a benzyl radical.Preferred quaternary ammonium hydroxides thus includebenzyldimethyldodecylammonium hydroxide, benzyldimethylteradecylammoniumhydroxide, benzyldimethylhexadecylammonium hydroxide,benzyldimethyloctadecylammonium hydroxide, and the like. Other suitablequaternary ammonium hydroxides include dimethylcyclohexyloctylammoniumhydroxide, diethylcyclohexyloctylammonium hydroxide,dipropylcyclohexyloctylammonium hydroxide,dimethylcyclohexyldecylammonium hydroxide,diethylcyclohexyldecylammonium hydroxide,dipropylcyclohexyldecylammonium hydroxide,dimethylcyclohexyldodecylammonium hydroxide,diethylcyclohexyldodecylammonium hydroxide,dipropycyclohexyldodecylammonium hydroxide,dimethylcyclohexyltetradecylammonium hydroxide,diethylcyclohexyltetradecylammonium hydroxide,dipropylcyclohexyltetradecylammonium hydroxide,dimethylcyclohexylhexadecylammonium hydroxide,diethylcyclohexylhexadecylammonium hydroxide,dipropylcyclohexylhexadecylammonium hydroxide,dimethylcyclohexyloctadecylammonium hydroxide,diethylcyclohexyloctadecylammonium hydroxide,dipropylcyclohexyloctadecylammonium hydroxide, and the like. Othersuitable quaternary ammonium hydroxides are described in U.S. Pat. No.4,156,641.

The alkali metal hydroxides and quaternary ammonium hydroxides of thisinvention, as well as the metal chelates, particularly the metalphthalocyanines, are readily disposed on the molecular sieve support.The alkali metal hydroxide may comprise at least about 10 wt. % of thecatalytic composite. In the sweetening process herein contemplated, thealkali metal hydroxide will preferably comprise at least about 25 wt. %of the said composite and the quaternary ammonium hydroxide willcomprise at least about 10 wt. % of said composite. In general, up toabout 25 wt. % metal phthalocyanine can be adsorbed on the molecularsieve support and still form a stable catalytic composite. A lesseramount in the range of from about 0.1 to about 10 wt. % generally formsa suitably active catalytic composite.

The alkali metal hydroxide, the quaternary ammonium hydroxide, and themetal chelate components can be disposed on the molecular sieve supportin any conventional or otherwise convenient manner. Said components canbe disposed on said support simultaneously from a common aqueous oralcoholic mixture thereof, or separately and in any desired sequence.The disposition process can be effected utilizing conventionaltechniques whereby the support in the form of spheres, pills, pellets,granules or other particles of uniform or irregular size or shape, issoaked, suspended, dipped one or more times, or otherwise immersed in anaqueous or alcoholic mixture to dispose a given quantity of the alkalimetal hydroxide, quaternary ammonium hydroxide, and metal chelatecomponents thereon. One preferred method involves the use of asteam-jacketed rotary dryer. The molecular sieve support is immersed inthe impregnating mixture contained in the dryer and the support istumbled therein by the rotating motion of the dryer. Evaporation of theliquid in contact with the tumbling support is expedited by applying aflow of nitrogen through the dryer. In any case, the resulting compositeis allowed to dry under ambient temperature conditions, or dried at anelevated temperature in an oven, or in a flow of hot gases, or in anyother suitable manner.

An alternative and convenient method for disposing the alkali metalhydroxide, quaternary ammonium hydroxide, and metal chelate componentson the molecular sieve support comprises predisposing the support in asour petroleum distillate treating zone or chamber as a fixed bed andpassing the alkali metal hydroxide-metal chelate-quaternary ammoniumhydroxide mixture through the bed in order to form the catalyticcomposite in situ. This method allows the mixture to be recycled one ormore times to achieve a desired concentration of the alkali metalhydroxide, quaternary ammonium hydroxide, and metal chelate componentson the molecular sieve support. In still another alternative method, themolecular sieve may be predisposed in said treating zone or chamber, andthe zone or chamber thereafter filled with the mixture of alkali metalhydroxide, metal chelate, and quaternary ammonium hydroxide to soak thesupport for a predetermined period.

Another alternative for disposing the alkali metal hydroxide, quaternaryammonium hydroxide, and metal chelate components on the molecular sievesupport comprises use of a quaternary ammonium salt instead of thequaternary ammonium hydroxide. The quaternary ammonium salt can beadmixed with the alkali metal hydroxide and metal chelate to form acommon aqueous or alcoholic mixture which can be used as indicated inthe previous two paragraphs. Alternatively, one quaternary ammonium saltcan be predisposed on the molecular sieve support by any conventional orotherwise convenient manner, and thereafter the alkali metal hydroxideand the metal chelate can be disposed on the molecular sieve support byany of the methods indicated in the previous two paragraphs. Suitablequaternary ammonium salts include halides, nitrates, nitrites, sulfates,phosphates, acetates, citrates, and tartrates, Halides are the preferredsalts. Because the mixing of the molecular sieves and the alkali metalhydroxide is exothermic, it is preferred to perform the mixing by meanswhich will maintain the temperature of the molecular sieves below theirfracture point. Further, mixing and drying temperatures should bemaintained below the temperature of thermal decomposition of theparticular quaternary ammonium hydroxide being used. In general,quaternary ammonium hydroxides are subject to thermal decomposition attemperatures above 100° C.

In the process of sweetening a sour petroleum distillate, it hasheretofore been the practice to oxidize the mercaptans contained thereinin the presence of an alkaline agent. With respect to the method of thisinvention, those distillates containing the more readily oxidizedmercaptans can be treated in the absence of added alkaline agent. A sourpetroleum distillate is passed in contact with the catalytic compositeof this invention. The catalytic composite can be dispersed within thedistillate, or it can be disposed as a fixed bed in a container. Thecontacting can be batch-type, or continuous. A continuous treatingoperation using a fixed bed of the catalytic composite is preferred. Anoxidizing agent, preferably air, is introduced to contact the distillateand the catalytic composite to provide at least the stoichiometricamount of oxygen required to oxidize the mercaptan content of thedistillate. It may be preferable in treating distillates with highmercaptan content to contact the catalytic composite with an alkalineagent prior to contacting the distillate and the catalytic composite.

Treatment of sour petroleum distillates in contact with the catalyticcomposite of this invention can be performed in the presence of analkaline agent as heretofore practiced, if desired. The catalyticcomposite is initially saturated with an alkaline agent, and an alkalineagent thereafter passed in contact with the catalyst bed, continuouslyor intermittently as required, admixed with the sour petroleumdistillate. Any suitable alkaline agent may be employed. An alkali metalhydroxide in an aqueous solution, e.g. sodium hydroxide in aqueoussolution, is most often employed. The solution may further comprise asolubilizer to promote mercaptan solubility, e.g. alcohol, andespecially methanol, ethanol, n-propanol, isopropanol, etc., and alsophenols, cresols, and the like. The solubilizer, when employed, ispreferably methanol, and the alkaline solution may suitably comprisefrom about 2 to about 100 vol. % thereof. Sodium hydroxide and potassiumhydroxide constitute the preferred alkaline agents. Others includinglithium hydroxide, rubidium hydroxide and cesium hydroxide are alsosuitably employed.

The method of treating of this invention can be effected in accordancewith prior art treating conditions. The process is usually effected atambient temperature conditions, although higher temperatures up to about105° C. are suitably employed. Pressures of up to about 1,000 psi ormore are operable, although atmospheric or substantially atmosphericpressures are entirely suitable. Contact times equivalent to a liquidhourly space velocity of from about 0.5 to about 10 or more areeffective to achieve a desired reduction in the mercaptan content of asour petroleum distillate, an optimum contact time being dependent onthe size of the treating zone, the quantity of catalyst containedtherein, and the character of the distillate being treated.

As previously stated, sweetening of the sour petroleum distillate iseffected by oxidizing the mercaptan content thereof to disulfides.Accordingly, the process is effected in the presence of an oxidizingagent, preferably air, although oxygen or other oxygen-containing gasmay be employed. In fixed bed treating operations, the sour petroleumdistillate may be passed upwardly or downwardly through the catalyticcomposite. The sour petroleum distillate may contain sufficiententrained air, but generally added air is admixed with the distillateand charged to the treating zone concurrently therewith. In some cases,it may be of advantage to charge the air separately to the treating zoneand countercurrent to the distillate separately charged thereto.

As heretofore mentioned, the alkali metal hydroxide, quaternary ammoniumhydroxide, and metal chelate components of the catalytic composite ofthis invention are readily adsorbed on the molecular sieve support.Thus, any of the said components which may in time be leached from thesupport and carried away in the reactant stream can be easily restoredto the catalytic composite in situ by introducing either or any of saidcomponents to the sweetening process, for example, in admixture with thedistillate being treated to be disposed on the support in the treatingzone.

The following examples are presented in illustration of certainpreferred embodiments of this invention and are not intended as unduelimitations on the generally broad scope of the invention as set out inthe appended claims.

EXAMPLE I

In this example, an actuated charcoal supported cobalt phthalocyaninemonosulfonate catalyst was prepared in accordance with prior artpractice by adsorbing the cobalt phthalocyanine monosulfonate on anactivated charcoal support from a methanolic dispersion thereof. Thus,150 mg. of cobalt phthalocyanine monosulfonate was admixed with 50 ml.of methanol and stirred for about 5 minutes. The resulting dispersionwas then further diluted to 300 ml. with methanol with an additional 5minutes of stirring. About 100 cc. of the activated charcoal particles,having an average bulk density of about 0.25 gm/cc and a particle sizein the 10×30 mesh range, was immersed in the methanol dispersion, andthe dispersion was stirred in contact with the particles for about 5minutes and then maintained in contact with the particles for 1 hourunder quiescent conditions. The methanolic dispersion was thereafterevaporated to dryness over a steam bath in contact with the charcoalparticles, and the resulting particles were subsequently oven dried at100° C. for 1 hour.

EXAMPLE II

This example illustrates one embodiment of this invention. A 50 wt. %solution of isopropyl alcohol and dimethyl benzyl-n-alkylammoniumchloride was prepared. The dimethylbenzyl-n-alkyl-ammonium chloridecomprised dimethylbenzyldodecylammonium chloride (61%),dimethylbenzyltetradecylammonium chloride (23%),dimethylbenzylhexadecylammonium chloride (11%), anddimethylbenzyloctadecylammonium chloride (5%). About 100 cc. of clean,dry 8×12 mesh molecular sieves were admixed with 10 wt. % of theforegoing substituted ammonium chloride. The molecular sieves were ofthe X-type, with an alumina-silicate base and an average pore size of 10Angstroms. The cation was sodium. The molecular sieves were maintainedin contact with the substituted ammonium chloride for approximately 60minutes. The admixture was thereafter evaporated to dryness over a steambath to form a composite. Thereafter, a mixture of 150 mg. of cobaltphthalocyanine monosulfonate and 150 ml. of 7 wt. % aqueous sodiumhydroxide was admixed with the aforesaid composite. The composite wasmaintained in contact with the aforesaid mixture for approximately 60minutes. The resulting admixture was thereafter evaporated to drynesswith a vacuum apparatus to form one embodiment of the catalyticcomposite of this invention.

EXAMPLE III

A comparative evaluation of the catalytic composite of the foregoingExample I and Example II was effected in the following manner. Thisexample illustrates another embodiment of this invention. In each case,100 cc. of the catalyst was disposed as a fixed bed in a vertical glasstubular reactor maintained at ambient temperature conditions--about 80°to 85° F. Air was charged to the system through a rotameter at about 200cc. per hour and admixed with a sour kerosene feedstock. The kerosenefeedstock contained 1028 ppm. mercaptan sulfur. The mixture wasprocessed downwardly through the catalyst bed at a liquid hourly spacevelocity of about 1 over a 20 hour period. The reactor effluent wasmonitored and analyzed periodically for mercaptan sulfur.

The Table below sets forth the results of the foregoing examples. Run Icorresponds to the run of Example III wherein the catalytic composite ofExample I was used. Run II corresponds to the run of Example III whereinthe catalytic composite of Example II was used.

                  TABLE                                                           ______________________________________                                                   Mercaptan Sulfur, wt. ppm.                                         Time, Hrs.   Run I         Run II                                             ______________________________________                                        0            1028          1028                                               1            372           158                                                5            475           118                                                10           500           161                                                15           496           181                                                20           500           291                                                ______________________________________                                    

The above results clearly indicate the superiority of the catalyticcomposite of this invention over a catalytic composite prepared in aconventional manner. The catalytic composite of Example II was moreeffective than the catalytic composite of Example I in treating a sourpetroleum distillate.

I claim as my invention:
 1. A catalytic composite comprising a metalchelate, an alkali metal hydroxide, and a quaternary ammonium hydroxidedisposed on a molecular sieve support, the quaternary ammonium hydroxiderepresented by the structural formula: ##STR4## wherein R is ahydrocarbon radical containing up to about 20 carbon atoms and selectedfrom the group consisting of alkyl, cycloalkyl, aryl, alkaryl andaralkyl, and R' is a substantially straight-chain alkyl radicalcontaining from about 5 to about 20 carbon atoms, said alkali metalhydroxide comprising at least about 10 wt. % of said catalyticcomposite.
 2. The catalytic composite of claim 1 wherein said molecularsieve is a Type X molecular sieve.
 3. The catalytic composite of claim 1wherein said molecular sieve is a Type X molecular sieve of the sodaform.
 4. The catalytic composite of claim 1 wherein said alkali metalhydroxide comprises at least about 20 wt. % of said catalytic composite.5. The catalytic composite of claim 1 wherein said alkali metalhydroxide comprises at least 20 wt. % of said catalytic composite andsaid quaternary ammonium hydroxide comprises at least 10 wt. % of saidcatalytic composite.
 6. The catalytic composite of claim 1 wherein saidalkali metal hydroxide is sodium hydroxide.
 7. The catalytic compositeof claim 1 wherein said alkali metal hydroxide is potassium hydroxide.8. The catalytic composite of claim 1 wherein said quaternary ammoniumhydroxide is dimethylbenzylalkylammonium hydroxide.
 9. The catalyticcomposite of claim 1 wherein said metal chelate is a metalphthalocyanine.
 10. The catalytic composite of claim 1 wherein saidmetal chelate is cobalt phthalocyanine.
 11. The catalytic composite ofclaim 1 wherein said metal chelate is cobalt phthalocyaninemonosulfonate.
 12. The catalytic composite of claim 1 wherein said metalchelate is vanadium phthalocyanine.
 13. A method of manufacture of acatalytic composite which comprises contacting a molecular sieve with ametal chelate, a quaternary ammonium hydroxide, and a mixture of alkalimetal hydroxide and at least one solvent selected from the groupconsisting of water and alcohols with fewer than 6 carbon atoms, at atemperature below the temperature of decomposition of said quaternaryammonium hydroxide, said alkali metal hydroxide present in said mixturein such amount that said alkali metal hydroxide comprises at least about10 wt. % of said catalytic composite, and said substituted ammoniumcompound represented by the structural formula: ##STR5## wherein R is ahydrocarbon radical containing up to about 20 carbon atoms and selectedfrom the group consisting of alkyl, cycloalkyl, aryl, alkaryl andaralkyl, R' is a substantially straight-chain alkyl radical containingfrom about 5 to about 20 carbon atoms.
 14. The method of claim 13wherein said molecular sieve is a Type X molecular sieve.
 15. The methodof claim 13 wherein said molecular sieve is a Type X molecular sieve ofthe soda form.
 16. The method of claim 13 wherein said alkali metalhydroxide comprises at least about 20 wt. % of said catalytic composite.17. The method of claim 13 wherein said alkali metal hydroxide comprisesat least 20 wt. % of said catalytic composite and said quaternaryammonium hydroxide comprises at least 10 wt. % of said catalyticcomposite.
 18. The method of claim 13 wherein said alkali metalhydroxide is sodium hydroxide.
 19. The method of claim 13 wherein saidalkali metal hydroxide is potassium hydroxide.
 20. The method of claim13 wherein said quaternary ammonium hydroxide isdimethylbenzylalkylammonium hydroxide.
 21. The method of claim 13wherein said metal chelate is a metal phthalocyanine.
 22. The method ofclaim 13 wherein said metal chelate is cobalt phthalocyanine.
 23. Themethod of claim 13 wherein said metal chelate is cobalt phthalocyaninemonosulfonate.
 24. The method of claim 13 wherein said metal chelate isvanadium phthalocyanine.